report on the kinetics (stopped-flow, -90 to 10 degrees C) of O2-binding to a series of dicopper(I) complexes, [Cu2(Nn)(MeCN)2]2+ (1Nn) (-(CH2)n- (n = 3-5) linked bis[(2-(2-pyridyl)ethyl]amine, PY2) and their close mononuclear analogue, [(MePY2)Cu(MeCN)]+ (3), which form mu-eta 2:eta 2-peroxodicopper(II) complexes [Cu2(Nn)-(O2)]2+ (2Nn) and [(MePY2)Cu]2(O2)]2+ (4), respectively. The overall kinetic mechanism
铜-二氧相互作用之所以引起人们的关注,是因为它们在
生物系统中作为可逆的O2载体,加氧酶或氧化酶的重要性,并且还因为它们在工业和实验室氧化过程中的作用。在这里我们报告的O2绑定到一系列的dicopper(I)配合物[Cu2(Nn)(MeCN)2] 2+(1Nn)(-(
CH2)n-(n = 3-5)连接的双[(2-(2-
吡啶基)乙基]胺,PY2)及其紧密的单核类似物[(MePY2)Cu(MeCN)] +(3),形成mu-eta 2:eta 2-peroxodicopper(II)络合物分别为[Cu2(Nn)-(O2)] 2+(2Nn)和[(MePY2)Cu] 2(O2)] 2+(4)。动力学机制涉及不可检测的中间O2-加合物[Cu2(Nn)(O2)] 2+(开放)的初始可逆(k +,开/ k-开放)形成,建议是CuI ... CuII-O2-物种,然后是其可逆闭合(k +,closed /